Silver halide light-sensitive photographic material

ABSTRACT

A silver halide light-sensitive photographic material is disclosed. The photographic material comprises a support and a blue-sensitive silver halide emulsion layer. The blue sensitive emulsion layer comprises a mixture of at least two kinds of silver halide emulsions each comprises silver chloride grains or silver chlorobromide grains containing not less than 90 mol % of silver chloride and are sensitized with a blue-sensitizing dye and have an average grain size of from 0.6 μm to 0.9 μm in terms of diameter of spherical grain. The average grain sizes of the two kinds of the emulsions are different from each other in the average grain size by 0.05 μm or more. The coating amount of the blue-sensitizing dye contained in the blue-sensitive emulsion layer is not more than 7.0×10 -4  g/m 2 .

This application is a continuation of application Ser. No. 08/124,314,filed Sep. 20, 1993, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a light-sensitive silver halidephotographic material for photo-printing. To be more specific. Thepresent invention relates to a color light-sensitive silver halidephotographic material which is excellent in gradation and of which iscapable of improving the productivity of printing process.

BACKGROUND OF THE INVENTION

Recently in the field of photographic print, for the purpose ofshortening delivery date and improving productivity of printing process,a method of shortening printing time has employed by using silver halidephotographic material with high silver chloride content and rapiddevelopment. However, since development speed of silver chloride isremarkably fast, it is found that it is difficult to maintain continuousgradation from highlight to shadow portions of the characteristic curve,and that the curve tends to irregularly bend depending upon theprocessing condition.

Against this disadvantage, a method, whereby it is possible to obtain acharacteristic curve with an expanded straight portion from highlight toshadow, by using a silver halide emulsion in which two or more kinds ofsilver halide grains with different sensitivities are mixed at asuitable ratio, has been proposed and the effect thereof has beenrecognised.

However, it has been found out when the method for improving gradationcharacteristics by mixing these emulsions, is applied, especially to asilver halide emulsion sensitized in the blue-light, variation in thegradation at the time of exposure is often seen against the change ofthe temperature, and thus improvement in the expansion of gradation,which is a main object of the present invention, cannot be achieved.

In view of the state of the art, the appearance of a light-sensitivesilver halide photographic material for print which is applicable torapid process and has improved gradation has long been waited.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a light-sensitivesilver halide photographic material which is excellent in gradation andstable against external environmental changes such as variations oftemperature at the time of exposure.

The silver halide light-sensitive material of the invention comprises asupport having thereon a blue-sensitive silver halide emulsion layer,comprising a mixture of at least two kinds of silver halide emulsionseach optically sensitized with a blue-sensitizing dye, wherein

(1) the silver halide emulsions each comprise silver chloride grains orsilver chlorobromide grains having a silver chloride content not lessthan 90 mol %,

(2) the silver halide emulsions each have an average grain size, interms of diameter of spherical grain being within the range of 0.6 μm to0.9 μm and being different from each other by 0.05 μm or more in theaverage grain size, and

(3) the coating amount of the blue-sensitizing dye is not more than7.0×10⁻⁴ g/m².

DETAILED DESCRIPTION OF THE INVENTION

Silver halide emulsion grain advantageously used in the presentinvention is one having a silver chloride content of 95-99.95 in termsof mol %. And, more preferably, it is a silver chlorobromide grain whichsubstantially contains no silver iodide. For the purpose of shorteningdeveloping time and lowering replenishing amount of the color developer,more preferable silver chloride content is 99.5-99.9 mol %.

As for the crystal shape of the silver halide grain used for thephotographic material of the present invention, an arbitary one may beused. According to one preferable embodiment of the present invention,cubic crystals having <100> faces can be mentioned. Moreover, silverhalide grains having an octahedral, tetradecahedral or dodecahedralcrystal shape, which may be prepared according to the method disclosed,for example, in U.S. Pat. Nos. 4,183,756 and 4,225,666, japanese PatentO.P.I Publications No. 55-26589 (1980), Japanese Patent Publication No.55-42737 (1980), Journal of Photographic Sciences Vols. No. 21 and39(1973), etc. may also be used. Farther, grains which have twin planecan also may be used.

Silver halide grains used for the light-sensitive photographic materialof the present invention may comprise of a single shape or a mixture oftwo or more grains of different shapes.

The grain size of the silver halide grains used for the light-sensitivephotographic material of the present invention falls within the rangebetween 0.6 and 0.9 microns in terms of diameter when the grain size isconverted into an equivalent projection circle.

In the photographic material of the present invention, in order torealize excellent gradation characteristics, it is preferable that thesilver halide emulsion is a mixture of two kinds of silver halideemulsions of which average grain size falls within the range between 0.6and 0.9 μm and the grain size difference between the respectiveemulsions is more than 0.05 μm. A preferable grain size difference isbetween a range of 0.07 and 0.15 μm. As a preferable example, a mixtureof two kinds of emulsions, of which average grain sizes are 0.7 μm and0.8 μm, respectively, at a ratio of 65:35 may be mentioned.

The above-mentioned grain size can be measured by various methods usedin the photographic field. As typical methods, those described in"Analytical Method for Particle Diameter Measurement" written byLoveland, Symposium on Light Microscopy, A.S.T.M., pp. 94-122(1955) andin "The Theory of Photographic Process, Vol.3" (Mees and James, andpublished by Mcmillan, 1966) can be mentioned.

When the grains consist substantially of a uniform shape, particle sizedistribution can be represented considerably accurately as a diameter oran equivalent projection area.

The grain size distribution of the silver halide grains used for thelight-sensitive photographic material of the present invention may beeither poly-dispersion or mono-dispersion. Preferably, mono-dispersesilver halide grains of which variation coefficient of size distributionis not more than 0.22 and, more preferably, not more than 0.15 may beadvantageous. Herein, the variation coefficient of grain sizedistribution is a factor representing the width of particle sizedistribution and is defined by the following equation.

    Variation Coefficient=S/R

In the above, R is standard deviation of particle size distribution andS is the average grain size. The grain size denotes the diameter in thecase of spherical silver halide grain and, in the case of the grains ofother shape than spherical like cubic grain, it stands for the diameterwhen the projection image thereof is converted into a circle havingequivalent area.

As for preparation of the silver halide emulsion used in the presentinvention, various methods and equipments which are well known in theart may be employed.

The silver halide emulsion used in the present invention can be the oneprepared by either an acid process, a neutral process or an ammonicalprocess. The silver halide grains in the emulsion may be the ones havingbeen grown up either at a time or after forming seed grains. As for themethod of making the seed grains and the method for growing the same, itmay be either the same or different.

As for the manner of reacting the water-soluble silver salt with thewater-soluble halide, either normal precipitaion method, reverseprecipitation method, double-jet method, or any combination thereof mayoptionally be employed, the double-jet mixing method is preferable.Furthermore, as one form of the double-jet method, a method so-called"pAg-controlled double-jet process" described in Japanese Patent O.P.I.Publication No. 54-48521(1979) may also be employed.

Furthermore, an equipment provided with an additional solution-supplyingequipment arranged in the mother reaction solution, from which thewater-soluble silver salt and the water-soluble halide salt aresupplied, which is described in Japanese Patent O.P.I. Publications No.57-92523(1982) and 57-92524(1982). An equipment as described in theGerman OLS Patent Publication No. 2921164, in which the water-solublesilver salt solution and the water-soluble halide salt solution areadded, while continuously changing the concentration of the salts and anequipment. Further an equipment may also be used in which the silverhalide grains are formed while keeping the distance between the silverhalide grains constant and taking out the reaction mother solution fromthe reaction vessel and condensing it by ultrafiltration method, whichis described in Japanese Patent Publication No. 56-501776(1981).

Moreover, if necessary, a silver halide solvent such as the thioethercan be used. Further, a compound having a mercapt group, anitrogen-containing heterocyclic compound or a compound like a opticalsensitizer may be added at the time or after completion of the formationof silver halide grains.

For the purpose of reduction sensitizing the silver halide emulsion usedin the present invention, various conventional methods can be applied.For instance, a method of adding various reducing agents, a ripeningmethod under condition of high silver ion concentration or high pH canbe used.

When the silver halide emulsion used in the present invention undergoessulfur sensitization, as the sulfur sensitizing agent, thiosulfate, anallylthiocarbazide, thiourea, an allyl iso-thiocyanate, cystine,p-toluene thiosulfate, rhodanin and an elemental sulfur, can bementioned. Other than the above, those sulfur sensitizers described inU.S. Pat. Nos. 1,574,944; 2,410,689 and 2,278,974 can also be used. Theadding amount of the sulfur sensitizing agent changes over the rangeconsiderably depending upon pH, temperature, and various otherconditions such as the size of silver halide grains, etc. As the generalstandard, a range from about 10⁻³ mols to 10⁻⁷ mols per mol of silverhalide mol is preferable. More preferably, it is in the range between10⁻⁶ and 10⁻⁵ mols.

It is preferable that the silver halide emulsion used in the presentinvention is undergone the gold sensitization. As the gold sensitizer,various gold complexes such as chloroaurate, auric sulfide and auricthiosulfate may be used as a ligand compound used, for example, dimethylrhodanin, thiocyanate, mercapto tetrazole, mercapto triazole can bementioned. Preferable amount of use of the gold compound changesdepending upon the kind of the emulsion or the compound to be used andvarious other conditions such as ripening conditions. The amount isusually preferable within the range of 1×10⁻⁸ to 1×10⁻⁴ mol, morepreferably, it is the range beween 1×10⁻⁵ and 1×10⁻⁸ mols per mol ofsilver halide.

Furthur, reduction sensitization or noble metal sensitization canoptionally be employed together with the sulfur sensitization methodmentioned above.

As spectral sensitizing dyes suitably used for the blue-sensitive silverhalide emulsion of the present invention, any conventionally knowncompounds can be used. The compound shown by following formulae 1 and 2is especially useful as the blue light-sensitive sensitizing dye. Thesedyes can be used either singly or in combination. ##STR1## wherein Z₁and Z₂ independently represent a group of atoms necessary to complete athiazole ring, a benzthiazole ring, benzselenazole ring, anaphthothiazole ring or a naphthoselenazole ring; R1 and R2independently represent an aliphatic group or an aliphatic groupcontaining therein an carboxylic group or a sulfo group provided that atleast one of R₁ and R₂ is an aliphatic group having acarboxylic group ora sulpho group. At least one of R1 and R2 represents an aliphatic groupwhich contains a carboxyl group or the sulfo group and one otherrepresents an aliphatic group. X1 represents an acid anion and mrepresents an integer of 0 or 1. ##STR2## wherein Z₃ and Z₄independently represent an atomic group necessary to complete a thiazolering, a benzthiazole ring or a benzselenazole ring; R₃ and R₄independently represent an aliphatic group or an aliphatic groupcontaining therein an carboxylic group or a sulfo group provided that atleast one of R₃ and R₄ is an aliphatic group having a carboxylic groupor a sulpho group; X₂ represents an acid anion and m represents aninteger of 0 or 1.

It is preferable that the blue-sensitive emulsion used in the inventionis optically sensitized with a compound represented by theafore-mentioned Formula 1 and a compound represented by Formula 2.

In the above-mentioned Formula 1, the ring represented by Z₁ and Z₂ mayhave a substituent at the position other than at the nitrogen atom. Thesubstituent includes, for example, a halogen atom such as chlorine,bromine, and fluorine an alkyl group containing one to four carbon atomssuch as methyl, ethyl, propyl; an alkoxy group containing one to fourcarbon carbons such as methoxy, ethoxy; a hydroxyl group, a carboxylgroup, an alkoxycarbonyl group such as ethoxycarbonyl group; asubstituted alkyl group such as tri-fluoro methyl group, benzyl group,fenetyl group; an aryl group such as phenyl group; or a substituted arylgroup such as p-tolyl group.

R₁ and R₂ independently represent an aliphatic group having one to eightcarbon atoms. They include saturated and unsaturated aliphatichydrocarbon groups. The carbon chain of the aliphatio hydrocarbon groupmay be interrupted by a hetero atom such as oxygen, sulfur, nitrogen,and the substituent includes, for example, hydroxyl group, an alkoxygroup, an alkylcarbonyloxy group, a phenyl group and a substitutedphenyl group, a carboxyl group, a sulfo group. Herein, at least one ofR₁ and R₂ has a carboxyl group or a sulfo group. When both R₁ and R₂have a carboxyl group or a sulfo group, one of them may form anintramolecular salt with a cathion such as an alkali ion or an organicbase onium ion.

In Formula 2, the ring formed including Z₃ and Z4 may have a substituentother than R₃ and R₄ on the nitrogen atom. The substituent includes, forexample, a halogen atom such as chlorine, bromine, and fluorine; analkyl group containing one to four carbon atoms such as methyl, ethyl,propyl; an alkoxy group containing one to four carbon arbons such asmethoxy, ethoxy; a hydroxyl group, a carboxyl group, an alkoxycarbonylgroup having one to four carbon atoms such as ethoxycarbonyl group; asubstituted alkyl group such as tri-fluoro methyl group, benzyl group,fenetyl group; an aryl group such as phenyl group; or a substituted arylgroup such as p-tolyl group; R₃ and R₄ respectively represent the samegroup as R₁ and R₂ in Formula 1, and at least one of R₃ and R₄ is analiphatic group containing a carboxyl group or a sulfo group.

These dyes represented by the Formula 1 and Formula 2 are respectivelyknown compounds and they may easily be synthesized by one skilled in theart with reference to the description in, for example, U.S. Pat. Nos.3,149,105 and 2,238,231; British Patent No. 742,112 and on page 55 etseq. of "The Cyanine Dyes and Related Compounds" written by M. Harmerand published by Interscience Publisher, New York (1964).

Typical example of the sensitizing dyes useful in the present invention,represented by the Formula 1 and Formula 2 are shown below. ##STR3##

The amount of the blue-sensitizing dye is important for achieving theobject of the present invention. It is found that when the amountexceeds 7.0×10⁻⁴ g/m² in the lightsensitive material constituted, thegradation variation depending on the variation in temperature wasremarkable in the light-sensitive material with a blue-sensitiveemulsion layer comprising the mixture emulsion of two kinds or more.

Therefore, the amount of the blue-sensitizing dye may be less than7.0×10⁻⁴ g/m² and may be decided in the light of sensitivity of theemulsion. Practically, the range between 4.0×10⁻⁴ and 7.0×10³¹ 4 g/m² ispreferable from the viewpoint of productivity of the automatic printingprocess.

The sensitizing dye may be added to the emulsion at the arbitary timeduring preparation of the emulsion, either during or after completion ofthe precipitation, at the beginning, during or after completion ofchemical ripening, or before coating. Also, it may be added either atone time or after dividing it into two or more parts. The coating amountof the blue-sensitive emulsion layer is preferably 0.2 to 0.4 g/m², morepreferably 0.1 to 0.3 g/m², in terms of silver.

The present invention is preferably applied to a color photographiclight-sensitive material, particularly to a color photographic printingmaterial. In such case, the light-sensitive material has agreen-sensitive emulsion layer containing a green-sensitizing dye and ared-sensitive emulsion layer containing a red-sensitizing dye further tothe blue-sensitive emulsion layer.

As green and red sensitizing dyes, for example, compounds B-1 throughB-11 and compounds C-11 through C-14 and D-1 through D-8 described in JPO.P.I. Publication 1-216341(1989) preferably be used. When thelight-sensitive silver halide photographic material of the presentinvention is exposed in the printer using a semiconductor laser, it isnecessary to use a sensitizing dye which has light-sensitive in theinfrared. As for infra-red sensitizing dye, for example, compounds IRS-1through IRS-11 described on pp 12-14 of Japanese Patent O.P.I.Publication No. 4-285950(1992) may preferably be used. Moreover, it isadvantageous that supersensiting agents SS-1 through SS-9 described onpages 14 and 15 of the same is used together with these dyes. In thesilver halide emulsion of the present invention various known additivessuch as anti-foggants and stabilizing agents may be used for the purposeof, for example, preventing fog caused during preparation or storage ofthe silver halide photographic light-sensitive material or duringdevelopment process.

Example of compound which can be used for such objects. The compoundrepresented by Formula (II) described on page 7 column below in JapanesePatent O.P.I. Publication No. 2-146036(1990) can be mentioned. Asspecific examples, compounds (IIa-1) through (IIa-8), (IIb-1) through(IIb-7) and 1-(3-methoxyphenyl)-5-mercapto tetrazoles are preferable.

Among these compounds, the compound shown by the following Formula 3 isespecially preferable. ##STR4##

In the formula, Ar represents an aromatic residue and R₁ represents a--OR₂ group, a --N(R₃)SO₂ R₄ group or a --COOM₂ group; R₂ represents ahydrocarbon group having two or more of carbon atoms; R₃ represents ahydrogen atom or a hydrocarbon group; and R₄ represents a hydrocarbongroup and M₁ and M₂ independently represent a hydrogen atom, an alkalimetal atom, the alkaline earth metal atom or an ammonium group.

In Formula 3, Ar represents an aromatic group such as, for example, aphenyl group, a naphthyl group, a piridyl group. These aromatic groupscan have a substituent. The effect of the present invention isremarkable when Ar is a phenyl group.

In Formula 3, R₁ represents a --OR₂ group or a --N(R₃)SO₂ R₄ group or a--COOM₂ group. R₂, represents a hydrocarbon group having two or more ohcarbon atoms and it includes, for example, an alkyl group such as ethylgroup, hexyl group or dodecyl groups or an aryl group such as m-methoxyphenyl group, o-methoxy phenyl group. The effect of the presentinvention is remarkable when R₂ is an alkyl group and is preferable.Moreover, it is preferable that R₁ is a --N(R₃)SO₂ R₄ group or a --OR₂group and --N(R₃)SO₂ R₄ group is especially preferable.

R₃ represents a hydrogen atom or a hydrocarbon group such as methylgroup and other groups defined as R₂. The effect of the presentinvention is remarkable when R₃ is hydrogen atom.

R₄ represents a hydrocarbon group such as, for example, the samehydrocarbon groups as given for R₃. The effect of the present inventionis remarkable when R₃ is an alkyl group and is advantageous.

In Formula 3, M₁ and M₂ independently represent a hydrogen atom, analkali metal atom or an alkaline earth metal atom or an ammonium group.As the example of the metallic atom. Sodium, lithium, potassium, calciumcan be mentioned. When the metallic atom is of di-valent or more, ananion bonds to neutralize the electric charge. The effect of the presentinvention is remarkable when M₁ is a hydrogen atom and is preferable.

The compounds represented by Formula 3 is specifically shown below.

    ______________________________________                                        No.        R                                                                  ______________________________________                                         ##STR5##                                                                      1         OCH.sub.2 CH.sub.3                                                  2         O(CH.sub.2).sub.3 CH.sub.3                                          3         O(CH.sub.2).sub.5 CH.sub.3                                          4         O(CH.sub.2).sub.7 CH.sub.3                                          5         O(CH.sub.2).sub.11 CH.sub.3                                         6                                                                                        ##STR6##                                                           7                                                                                        ##STR7##                                                           8                                                                                        ##STR8##                                                           9                                                                                        ##STR9##                                                          10                                                                                        ##STR10##                                                         11         OCH.sub.2 CHCH.sub.2                                               12         OCH.sub.2 CCH                                                      13         NHSO.sub.2 CH.sub.3                                                14         NHSO.sub.2 (CH.sub.2).sub.3 CH.sub.3                               15         NHSO.sub.2 CH(CH.sub.3 ).sub.2                                     16                                                                                        ##STR11##                                                         17         NHSO.sub.2 CH.sub.2 CF.sub.3                                       18         NHSO.sub.2 (CH.sub.2).sub.3 Cl                                     19                                                                                        ##STR12##                                                         20                                                                                        ##STR13##                                                         21                                                                                        ##STR14##                                                         22         NHSO.sub.2 CH.sub.2 CHCH.sub.2                                     23         NHSO.sub.2 CH.sub.2 CCH                                            24         NHSO.sub.2 N(CH.sub.3).sub.2                                       25         NHSO.sub.2 (CH.sub.2).sub.7 CH.sub.3                               26         COOH                                                                ##STR15##                                                                    27         o-OCH.sub.2 CH.sub.3                                               28         o-O(CH.sub.2).sub.3 CH.sub.3                                       29                                                                                        ##STR16##                                                         30                                                                                        ##STR17##                                                         31         o-OCH.sub.2 CHCH.sub.2                                             32         m-OCH.sub.2 CH.sub.3                                               33         m-O(CH.sub.2).sub.5 CH.sub.3                                       34                                                                                        ##STR18##                                                         35                                                                                        ##STR19##                                                         36         o-NHSO.sub.2 CH.sub.3                                              37         o-NHSO.sub.2 (CH.sub.2).sub.2 CH.sub.3                             38                                                                                        ##STR20##                                                         39         o-NHSO.sub.2 CH.sub.2 CHCH.sub.2                                   40         m-NHSO.sub.2 CH.sub.3                                              41         m-NHSO.sub.2 (CH.sub.2).sub.3 CH.sub.3                             42         m-NHSO.sub.2 CH(CH.sub.3).sub.2                                    43                                                                                        ##STR21##                                                         44                                                                                        ##STR22##                                                         45         m-NHSO.sub.2 N(CH.sub.3).sub.2                                     46         m-NHSO.sub.2 (CH.sub.2).sub.7 CH.sub.3                             47         m-COOH                                                             48         m-COONa                                                            49                                                                                        ##STR23##                                                         50                                                                                        ##STR24##                                                         51                                                                                        ##STR25##                                                         52                                                                                        ##STR26##                                                         ______________________________________                                    

These compounds can be prepared with reference to the descriptiondisclosed in, for example, Journal of Chemical Society 49,1748 (1927);Journal of Organic Chemistry 39,2469(1965); Japanese Patent O.P.I.Publication No. 50-89034 (1975); Ann. Chim. 44-3, (1954); JapanesePatent Publication No. 40-28496(1965); Chem. Ber., 20,231(1887) and U.S.Pat. No. 3,259,976.

Dye-forming coupler used for the color light-sensitive materialaccording to the present invention is usually selected so that the dyewhich absorbs light of the emulsion layer photosensitive and thespectrum to each emulsion layer is formed. A magenta dye-forming coupleris used in the green-sensitive emulsion layer; a yellow dye-formingcoupler in the blue-sensitive emulsion layer and a cyan dye-formingcoupler is used in the red-sensitive emulsion layer. However, dependingupon the object the color light-sensitive material may be formed basedon the system different from the above-mentioned combination.

In the present invention, acyl acetanilide type couplers can preferablybe used as a yellow dye-forming coupler. Among acetanilide yellowdye-forming couplers, a benzoyl acetanilide type and a pivaloylacetanilide type compound are advantageous.

Hereafter, specific examples of the yellow-dye-forming couplerpreferably used in the present invention are given: ##STR27##

Besides the above-mentioned compounds exemplified compounds Y-1 throughY-146 disclosed on pages 7 through 16 in Japanese Patent O.P.I.Publication No. 63-85631(1988); exemplified compounds Y-1 through Y-98disclosed on pages 6 through 10 in Japanese Patent O.P.I. PublicationNo. 63-97951(1988); exemplified compounds Y-1 through Y-24 disclosed onpages 18 through 20 in Japanese Patent O.P.I. Publication No.1-156748(1989); exemplified compounds I-1 through I-50 disclosed onpages 4 through 7 in Japanese Patent O.P.I. Publication No.2-298943(1990) and exemplified compounds Y-1 through Y-48 disclosed onpages 114 through 120 in Japanese Patent O.P.I. Publication No.62-215272(1987) can also be used.

Other than yellow dye-formig couplers used in the silver halidelight-sensitive photographic material of the present invention, magentacoupler having its spectral absorption maximum in the wavelength rangebetween 500 nm and 600 nm and cyan coupler having its spectralabsorption maximum in the wavelength range between 600 nm and 750 nm arewell known in the art.

As magenta coupler which can be preferably used in the colorlight-sensitive material according to the present invention, ExemplifiedCompounds 1 through 223 disclosed on pages 18 through 32 in JapanesePatent O.P.I. Publication No. 62-66339(1987); Exemplified Compounds M-1through M-223 disclosed on pages 5 and 6 in Japanese Patent O.P.I.Publication No. 2-100048(1989); Exemplified Compounds M-1 through M-223disclosed on pages 5 and 6 in Japanese Patent O.P.I. Publication No.2-100048 (1989); Exemplified Compounds M-1 through M-30 disclosed onpages 9 through 26 in Japanese Patent O.P.I. Publication No. 3-214155(1991) and Exemplified Compounds M-1 through M-47 disclosed on pages 104through 114 in Japanese Patent O.P.I. Publication No. 62-215272(1987);can be mentioned.

As cyan coupler which can be preferably used in the silver halidelight-sensitive photographic material of the present invention, forexample, couplers represented by the general Formulae (C-I) and (C-II)disclosed in Japanese Patent O.P.I. Publication No. 4-114154(1992) canbe mentioned. To be more specific, Exemplified compounds CC-1 throughCC-9 disclosed on pages 18 through 21 in the same may be mentioned.

In the light-sensitive material of the present invention, various dyeshaving absorption in various wavelength resions can be used for thepurposes of anti-irradiation and anti-halation. Any well-known compoundscan be used fo this purpose. Especially, as a dye which has absorptionin the visible spectral region, dyes AI-1 through AI-11 disclosed onpages 117 and 118 in Japanese Patent O.P.I. Publication No.3-251840(1991) are preferable. As infra-red rays absorption dyes, thosedyes represented by the general Formulae (I), (II) and (III) on column 2below on page 2 of Japanese Patent O.P.I. Publication No. 1-280750 arepreferable in view of absorption characteristics and less photographiceffects upon the silver halide emulsion and stains by the residual dye.As specific examples, Exemplified Compounds (1) through (45) on theleftcolumn below on pages 3 thru page 5 can be mentioned.

When a dye-forming coupler used for the silver halide light-sensitivephotographic material of the present invention is added to photographicemulsion by oil protect emulsification process, after dissolving adye-forming coupler in a warer-immiscible high boiling point organicsolvent and, if necessary, together with a low boiling point organicsolvent and an water-soluble organic solvent, the mixture isemulsion-dispersed in a hydrophilic binder such as gelatin using asurface active agent to form an oil in water type dispersion. Asdispersing means, a stirring machine, a homogenizer, a colloid mill, aflow jet mixer, and a ultrasonic homogenizer can be used. A step ofeliminating the low boiling point organic solvent may be put during orafter emulsification process. As high boiling point organic solventwhich can be used to dissolve coupler and to disperse the dye-formingcoupler, phthalic acid esters such as di-octyl phosphate and phosphatessuch as tri-cresyl phosphate can be mentioned. Among these, phthalicacid ester can exert the effect of the present invention moreeffectively. Moreover, in stead of the method of using the high boilingpoint organic solvent, a method in which a coupler and a certainpolymeric compound, which is immiscible with water and soluble in theorganic solvent, are dissolved, if necessary, in a low boiling pointorganic solvent and/or in a water-soluble organic solvent and then themixture is emulsified by various dispersion means and using a surfactantin a hydrophilic binder such as aqueous gelatin solution, may also beemployed. As a polymer which is soluble in the organic solvent andinsoluble in water, water-insoluble used at this time, poly(N-t-butylacrylic amide) can be mentioned. For the purpose of shifting theabsorption wave length of the dye, compound (d-11), (A'-1) disclosed onpages 33 and 35 of Japanese Patent O.P.I. Publication No. 4-114154(1992)can also be used.

Moreover, the fluorescent dye-releasing compound disclosed in U.S. Pat.No. 4,774,187 may also be used.

As coating amount of coupler, there is especially no limitation, if anenough, density can be obtained. The coupler is used within 1×10⁻³ to 5mols per mol of silver halide and, more preferably, in the rangesbetween 1×10⁻² to 1 tool.

In the silver halide light-sensitive photographic material of thepresent invention, it is advantageous to use gelatin as a binder,however, if necessary, other hydrophilic colloids such as gelatinderivatives graft polymer of gelatin and synthesic high polymers,hydrophilic materials such as protein other than gelatin, sach as sugarderivatives, cellulose derivatives, and other hydrophilic homopolymersor copolymers can optionally be used.

As a reflective support used in the present invention any conventionalmaterial can be used. It includes, for example, white pigmentcontaining-polyethylene coated paper, baryta paper, vinyl chloridesheet, and white pigment containing-polyethylene terephthalate support.Among these, a support having polyolefine resin layer containing a whitepigment is preferable.

As white pigments used for the reflective support used in the presentinvention, inorganic/or organic white pigments preferably, inorganicwhite pigments can be used. For example, sulfates of alkali earth metalsuch as barium sulfates; carbonates of alkaline earth metal such ascalcium carbonate; silicas such as mote silicic acid and syntheticsilicates; silicic acid calcium, alumina, alumina hydrate, titaniumoxide zinc oxide, talc, and clay can be mentioned.

Among these, preferable white pigments are barium sulfate and titaniumoxide. Amount of white pigments comprised in the water resistive resinlayer on the surface of the reflective support of the present invention,10% or more by weight as the content in water resistance resin layer ispreferable. The content of more than 13% by weight is more preferableand 15% or more by weight is especially preferable.

Dispersion degree of the white pigment in the water resistive layer canbe determined by the method described in Japanese patent O.P.I.Publication No. 2-28640(1990). The dispersion degree of white pigmentsis preferable to 0.20 or less as the coefficient of variation of thedescription of the publication, more preferably 0.15 or less and 0.10 orless is most preferable when measured in this method.

If necessary, the silver halide light-sensitive photographic material ofthe present invention may ungergo any suitable surface treatment such ascorona discharge, ultraviolet ray irradiation, a flame treatment, etc.on the surface of the support. Afterwards, the photographic layer iscoated on the support directly or through one or more subbing layers,which are usually provided in order to improve various surfaceproperties of the support e.g., adhesion property, anti-static property,dimensional stability, abrasion resistance, hardness, anti-halation, andanti-friction characteristics.

Upon coating the photographic layers including the silver halideemulsion, a thickener may be used to improve the coating performance. Asthe coating method, extrusion coating and the curtain coating, wherebytwo or more kinds of photographic layers can be coated simultaneously,are especially useful.

In the processing of the silver halide light-sensitive photographicmaterial of the present invention as the color developing agent used forthe color developer, various aminophenol and p-phenylene diaminecompounds, which are widely used in the field of color photography, areused. Especially, aromatic primary amine type color developing agent ispreferably used.

As the aromatic primary amino developing agent, the following compoundscan be mentioned:

(1) N,N-dimethyl-p-phenylenediamine hydrochloride

(2) N-methyl-p-phenylenediamine hydrochloride

(3) 2-amino-5-(N-ethyl-N-dodecylamino)toluene

(4) N-ethyl-N-(β-methansulfonamide-ethyl)-3-methyl-4-(aminoaniline)sulfate

(5) N-ethyl-N-(β-hydroxyethyl-3-methyl-4-aminoaniline sulfate

(6) 4-aminoh-3-methyl-N,N,-diethyl aniline

(7) 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methyl anilinep-toluenesulfonate

(8) 4-amino-N-ethyl-N-(γ-hydroxypropyl)-3-methyl anilinep-toluenesulfonate

It is preferable that these color developing agents are used within therange between 1×10⁻³ and 2×10⁻¹ mols per liter of the developer and,more preferably, within the range between 5×10⁻³ and 2×10⁻¹ mols.

To the color developer, various known developer additives can be addedin addition to the above-mentioned color developing agent. Theseadditives include, for example, development retarder having pH bufferingaction such as alkali agent, chloride ion, and benz-triazole compounds,preservatives, and chelating agent. As the alkali agent used for thecolor developer in the present invention, for example, potassiumcarbonate, potassium borate and sodium tri-phosphate are included.Farther, for the purpose of pH adjustments, sodium hydroxide, potassiumhydroxide can be used. The pH value of the color developer is usuallybetween the range 9 to 12 and, more preferably, between 9.5 to 11.

For the purpose of development inhibition, halide is usually used. In arapid processing due to the necessity for the development to complete ina very short time, chloride ion such as potassium chloride, sodiumchloride are usually used. The amount of the chloride ion to be used isapproximately not less than 3.0×10⁻² mols and, more preferably, betweenthe range of 4.0×10⁻² and 5.0×10⁻¹ mols per liter of the developer.

The bromide ion can be used at an optional amount as far as it does notjeopardise object of the present invention, usually not more than1.0×10⁻³ mols per liter of the color developer and, more preferably, notmore than 5.0×10⁻⁴ mols is preferable.

As a preservative, hydroxylamine derivatives except hydroxyl amine,hydroxamic acids, hydrazines, hydrazidaminoketons, saccharoids,monoamines, diamines, polyamines, quaternary ammonium salts, nitroxyradicals, alcohols, oximes, diamido compounds, cyclic a mine compoundsare especially effective. Di-alkyl hydroxylamines such asdiethylhydroxylamine; alkanolamines such as triethanolamine areparticularly preferable.

As chelating agent used in the color developer, compounds such asaminopolycarboxylic acids, aminopolysulfonic acids, alkylsulfonic acidsand phosphonocarboxylic acids are used. ethylenediamine-tetraaceticacid, nitrylotriacetic acid, diethylenetriaminepentaacetic acid and1-hydroxyethylidene-1,1-disulfonic acid are particularly preperable.

Developing temperature is ordinary 15° C. or more, generally within therange of from 20° to 50° C. For rapid processing, a temperature of 30°C. or more is preferable.

Time for color development is ordinary 10 seconds to 4 minutes. In therapid processing, a time of 10 seconds to 1 minute is preferable. Whenmore rapid processing id required, it is preferable to perform thedevelopment for a time of 10 to 30 seconds.

In the processing, a method may be used, in which the color developer iscontinuously replenished accompanied with the running of the processing.In such case, it is preferable considering environmental pollution byoverflow of the developer that the replenishing amount to the developeris decided so as that the developer is not overflown during processing.The preferable replenishing amount of the developer is concretely 20 to60 ml/m² of processed photographic material.

The photographic light-sensitive material of the invention is subjectedto bleaching and fixing treatment after the development. The bleachingtreatment may be carried out with the fixing treatment at the same time.Washing is ordinary applied to the photographic material after fixing.Stabilizing treatment may be applied instead of the washing. Forprocessing the photographic material of the invention, aroller-transport type processor, in which the photographic material istransported by rollers quipped in processing tanks thereof, or anendless belt type processor, in which the photographic material is fixedon an endless belt and transported by the belt, may be used. Further, aprocessor having processing tanks in a form of slit may also be used, inwhich the photographic material is transported in the slit with aprocessing solution supplied to the slit.

EXAMPLE Example 1

High density polyethylene layers were laminated on the both surfaces ofa raw having a weight of 180 g/m² to make a reflective paper support. Inthe laminated layer provided on the side of the support, on which anemulsion layer to be coated, surface-treated anatase type titanium oxideis dispersed in a ratio of 15 weight percent. On the reflective support,layers each having the following composition were coated to prepareSamples 101 to 130. The coating solutions were prepared as follows.

In 60 ml of ethyl acetate 26.7 g of yellow coupler Y-1, 10 g of dyeimage stabilizer ST-1, 6.67 g of dye image stabilizer ST-2, o, 67 g ofadditive HQ-1 and 6.67 g of high-boiling solvent NDP were added anddissolved. The solution was dispersed in 220 ml of 10 % gelatin solutioncontaining 9.5 ml of 15 % solution of surfactant SU-1 by an ultrasonichomogenizer to prepare a yellow coupler dispersion. The dispersion ismixed with a blue-sensitive silver halide emulsion containing 8.68 g ofsilver which was prepared in the following conditions. Further, 6.7 mlof 5 % solution anti-irradiation dye and compounds and gelatin given inTable 3 were added to the solution to prepare a coating solution of thefirst layer. Coating solutions each to be coated as the second toseventh layers were prepared in the manner similar to that in thepreparation of the first layer coating solution. Compounds H-1 and H-2were added as hardeners to the second and forth layers, respectively.Surfactants SU-2 and SU-3 were added to control the surface tension ofcoating solution.

The compositions of layers were as follows:

    ______________________________________                                                                     Added amount                                     Layer     Composition        (g/m.sup.2)                                      ______________________________________                                        7th Layer Gelatin            1.00                                             (Protective                                                                             F-1                 0.002                                           layer)                                                                        6th layer Gelatin            0.40                                             (UV absorbing                                                                           UV absorbent UV-1  0.10                                             layer)    UV absorbent UV-2  0.04                                                       UV absorbent UV-3  0.16                                                       Anti-stain agent HQ-1                                                                            0.01                                                       DNP                0.20                                                       PVP                0.03                                                       Anti-irradiation dye AI-1                                                                        0.02                                             5th layer Gelatin            1.30                                             (Red-sensitive                                                                          Red-sensitive silver chloro-                                                                     0.21                                             layer)    bromide emulsion Em-R1                                                        Cyan coupler C-1   0.26                                                       Cyan coupler C-2   0.09                                                       Dye image stabilizer ST-1                                                                        0.20                                                       Anti-stain agent HQ-1                                                                            0.01                                                       HBS-1              0.20                                                       DOP                0.20                                             4th layer Gelatin            0.94                                             (UV absorbing                                                                           UV absorbent UV-1  0.28                                             layer)    UV absorbent UV-2  0.09                                                       UV absorbent UV-3  0.38                                                       Anti-stain agent HQ-1                                                                            0.03                                                       DNP                0.40                                                       Anti-irradiation dye AI-2                                                                        0.01                                             3rd layer Gelatin            1.40                                             (Green-   Green-sensitive silver chloro-                                                                   0.17                                             sensitive bromide emulsion Em-G1                                              layer)    Magenta coupler M-1                                                                              0.35                                                       Dye image stabilizer ST-3                                                                        0.15                                                       Dye image stabilizer ST-4                                                                        0.15                                                       Dye image stabilizer ST-5                                                                        0.15                                                       DNP                0.20                                             2nd layer Gelatin            1.20                                                       Anti-stain agent   0.12                                                       DIDP               0.15                                                       Anti-irradiation dye AI-3                                                                        0.01                                             1st layer Gelatin            1.20                                             (Blue-    Blue-sensitive silver chloro-                                                                    0.26                                             sensitive bromide emulsion shown in                                           layer)    Table                                                                         Yellow coupler Y-1 0.80                                                       Dye image stabilizer ST-1                                                                        0.30                                                       Dye image stabilizer ST-2                                                                        0.20                                                       Anti-stain agent HQ-1                                                                            0.02                                                       DNP                0.20                                             Support   Polyethylene-laminated paper                                        ______________________________________                                    

In the above, the amount of silver halide emulsion is described in termsof silver.

The addenda used in each layer were as follows:

H-i: Tetrakis(viylsulfonylmethyl)methane

H-2: Sodium 2,4-dichloro-6-hydroxy-s-triazine

SU-1: Sodium tri-iso-propylnaphthalenesulfonate

SU-2: Sodium di-(2-ethylhexyl) succinate

SU-3: Sodium di-(2,2,3,3,4,4,5,5-octafluropentyl) sulfosuccinate

DOP: di-octyl phthalate

DNP: di-nonyl phthalate

DIDP: Di i-decyl phthalate

PVP: Polyvinyl pyrrolidone

HBS-1: 1-4-(p-toluene sulfonamido)benzene

HBS-2:1 mixture of tri-(2-ethylhexyl)phosphate and tri-cresyl phosphatewith volume ratio of 2:1

HQ-1: 2,5-di-t-octyl hydroquinone

HQ-2: 2-hexadecyl-5-methyl hydroquinone

F-1: 5-chloro-2-methyl-iso-thiazoline-3-on ##STR28##

Preparation of Blue-Sensitive Silver Halide emulsion

Into 1000 ml of 2% aqueous gelatin solution, added simultaneously thefollowing Solution A and Solution B, of which temperature was kept at40° C., taking 30 minutes and controlling pAg and pH of the mixture at6.5 and 3.0, respectively.

Then Solution C and Solution D were added simultaneously to the mixturetaking 180 minutes and controlling pAg and pH of the mixture at 7.3 and5.5, respectively. And this time, pAg control was carried out accordingto the method discribed in Japanese Patent O.P.I. Publication No.59-45437(1984) and using aqueous solutions of sulfuric acid and sodiumhydroxide.

    ______________________________________                                        <Solution A>                                                                  Sodium chloride          3.42   g                                             Potassium bromide        0.07   g                                             Add water to make the total volume                                                                     200    ml                                            <Solution B>                                                                  Silver nitrate           10     g                                             Add water to make the total volume                                                                     200    ml                                            <Solution C>                                                                  Sodium chloride          102.7  g                                             Potassium bromide        2.10   g                                             Add water to make the total volume                                                                     600    ml                                            <Solution D>                                                                  Silver nitrate           300    g                                             Add water to make the total volume                                                                     600    ml                                            ______________________________________                                    

After completion of addition, the mixture was desalted using 5% aqueoussolution of Demol N (Product of Kao Atlas Co.) and 20% aqueous solutionof the magnesium sulfate and mixed with an aqeuous gelatin solution.Thus, mono-dispersed cubic grain emulsion EMP-1 of which average grainsize was 0.85 μm, coefficient of grain isze distribution variation(S/R), 0.07 and the silver chloride content was 99.0 mol % was obtained.

Further five kinds of blue-sensitive emulsions EMP-2 to EMP-7 wereprepared having each the average grain size of 0.55 μm, 0.65 μm, 0.75μm, 0.82 μm, 0.90 μm and 0.95 μm. respectively. These emulsions areprepared in the manner similar to the above-mentioned blue-sensitiveemulsion having 0.85 μm of grain size except that the adding time ofSolutions A and B and Solutions C and D were changed to obtaine 10, 20,24, 27, 35 and 40 minutes to the prescribed grain size. Thus obtainedthe blue-sensitive emulsions were mixed as described in Table and usedfor forming the blue-sensitive emulsion layer of the samples.

The emulsions EMP-1 to EMP-7 each were divided to 5 parts and underwentchemical ripeninga at 50° C., for optimum times using the followingcompounds, to obtain a blue-sensitive silver halide emulsions Em-B1 toEm-B7.

Emulsion EMP-1 to EMP-7 were each divided to 5 parts and chemicallsensitized with the following compounds to obtaine blue-sensitiveemulsions Em-B1(a)-(e) to Em-B7(a)-(e).

    ______________________________________                                        Sodium thiosulfate                                                                              0.8 mg/mol AgX                                              Chloroaurate      0.5 mg/mol AgX                                              STAB-1 (stabilizer)                                                                             6 × 10.sup.-4 mol/mol AgX                             BS-1 (sensitizing dye)                                                                          Prescribed amount                                           ______________________________________                                    

The amounts of BS-1 added to the emulsions marked (a) through (e) wereeach 0.235 mg, 0.282 mg, 0.329 mg, 0376 mg and 0.423 mg per mol ofsilver so that the coating amount of the dye to be 0.5, 0.6, 0.7, 0.8and 0.9 mg/m² after each of the emulsions was coated as a blue-sensitiveemulsion layer of sample as shown in Table 1 emulsion.

Thus obtained emulsions were classified by grouping those each havingthe same amount of the dye. Two kinds of emulsions were selected fromthe same group and mixed to form a blue-sensitive emulsion layr of asample in the ratio of 4:6 or 3:7 as shown in Table 1.

Preparing Green-Sensitive Silver Halide Emulsion

Silver halide emulsion EPM-2 having average grain size 0.43 μm, acoefficient of variation (S/R) of 0.07 and a silver chloride content of99.0 mol % was obtained in the manner similar to that in the preparationof EPM-1 but changing the time of addition of Solution A, Solution B,Solution C and Solution D.

Then, emulsion EMP-2 underwent chemical ripening at 50° C., for 120minutes and using the following compounds, to obtain a blue-sensitivesilver halide emulsion Em-G1.

    ______________________________________                                        Sodium thiosulfate                                                                              1.5 mg/mol AgX                                              Chloroaurate      1.0 mg/mol AgX                                              STAB-1 (stabilizer)                                                                             6 × 10.sup.-4 mol/mol AgX                             GS-1 (sensitizing dye)                                                                          4 × 10.sup.-4 mol/mol AgX                             ______________________________________                                    

Preparing Red-Sensitive Silver Halide Emulsion

A mono-disperse cubic silver halide emulsion EMP-3 having an averagegrain size of 0.50 μm, a coefficient of variation (S/R) of 0.087 and asilver chloride content of 99.0 mol %, was obtained in the similar tothat in the preparation of EPM-1 but changing the time of addition ofSolution A, Solution B, Solution C and Solution D.

Then, the emulsion EMP-3 underwent chemical ripeninga at 60° C., for 90minutes and using the following compounds, to obtain a red-sensitivesilver halide emulsion Em-R1.

    ______________________________________                                        Sodium thiosulfate                                                                              1.8 mg/mol AgX                                              Chloroaurate      2.0 mg/mol AgX                                              STAB-1 (stabilizer)                                                                             6 × 10.sup.-4 mol/mol AgX                             RS-1 (sensitizing dye)                                                                          1 × 10.sup.-4 mol/mol AgX                             ______________________________________                                    

Samples 1 to 33 were prepared using thus obtained emulsions. In theblue-senitive layers of the samples, two kinds of the blue-senstiveemulsions each having different average grain size were used in theratio dsescribed in Table.

Sensitometry

The sample was subjected to the sensitometry by exposing through anoptical wedge by the conventional method and processing by the followingprocessing step. The sensitivity was defined as the reciprocal of theexposure amount necessary to form an image density of 0.75. Thegradation was defined as the average gradient between densities 0.5 to1.0 on the characteristic curve. The fog was defined by the density ofan unexposed sample which was processed in the following process in thatonly the color development in the processing step at the time of twotimes 90 seconds.

Temperature Variation at at the Time of Exposure

The atmosphere of the circumference of the sensitometer for thesensitometry and the sample has been changed. Humidity was constantlymade 50%, temperature was changed to 3 steps of 10° C., 20° C., 30° C.,and the sensitometry was done and the change of the gradation of thesample depending on the temperature was examined.

    ______________________________________                                        Processing step                                                               Processing step                                                                            Processing temperature                                                                        Time                                             ______________________________________                                        Color development                                                                          35.0 ± 0.3° C.                                                                      45 seconds                                       Bleaching fixation                                                                         35.0 ± 0.5° C.                                                                      45 seconds                                       Stabilization                                                                              30-34° C.                                                                              90 seconds                                       Drying       60-80° C.                                                                              60 seconds                                       ______________________________________                                    

The composition of the photographic processing solution is shown below.

    ______________________________________                                        Color developer                                                               Pure water                  800    ml                                         Triethylene diamine         2      g                                          Diethylene glycol           10     g                                          Potassium bromide           0.01   g                                          Potassium chloride          3.5    g                                          Potassium sulfite           0.25   g                                          N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-                                                    6.0    g                                          aminoaniline sulfate                                                          N,N-diethyl hydroxyl amines 6.8    g                                          Triethanolamine             10.0   g                                          Sodium diethylenetriaminepentaacetate                                                                     2.0    g                                          Stilbene fluorescent brightening agent (4,4'-diamino                                                      2.0    g                                          sulfonic acid derivative)                                                     Potassium carbonate         30     g                                          ______________________________________                                    

The whole quantity is assumed one liter adding water and it is adjustedto pH=10.10.

    ______________________________________                                        Bleach-fixer                                                                  Ferric ammonium diethylenetriaminepentaacetate                                                           65     g                                           dihydrate                                                                     Diethylenetriaminepentaacetic acid                                                                       3      g                                           Ammonium thiosulfate (70% aqueous solution)                                                              100    ml                                          5-amino-1,3,4-thiadiazole-2-thial                                                                        2.0    g                                           Ammonium sulfate (40% aqueous solution)                                                                  27.5   ml                                          ______________________________________                                    

The whole quantity is assumed one liter adding water and it is adjustedwith potassium carbonate or glacial acetic acid to pH=6.5.

    ______________________________________                                        Stabilizing solution                                                          Ortho-phenylphenol          1.0    g                                          5-chloro-2-methyl-4-isothiazoline-3-on                                                                    0.02   g                                          2-methyl-4-isothiazoline-3-on                                                                             0.02   g                                          Diethylene glycol           1.0    g                                          Fluorescent brightening agent (Chipanol SFP)                                                              2.0    g                                          1-hydroxyethylidene-1,1-diphosphonic acid                                                                 1.8    g                                          BiCl.sub.3 (45-% aqueous solution)                                                                        0.65   g                                          MgSO.sub.4 7H.sub.2 O       0.2    g                                          PVP (polyvinyl pyrrolidone) 1.0    g                                          Ammonia water (ammonium hydroxide 25% aqueous                                                             2.5    g                                          solution)                                                                     Tri-sodium nitriloacetate   1.5    g                                          ______________________________________                                    

The whole quantity is assumed one liter adding water and it is adjustedwith sulfuric acid or the ammonia water to pH=7.5.

The image density formed on the processed sample was measured with bluelight by PDA-65 densitometer (product of Konica Corp.). Following Table1 showed the result.

                                      TABLE 1                                     __________________________________________________________________________                      Mixing                                                                             Coating amount   Gradation by                                            ratio of                                                                           of blue-                                                                              Relative exposure at various                   Sample                                                                            Average grain size                                                                          Emulsion                                                                           sensitizing dye                                                                       Sensitiv-                                                                          Grada-                                                                            temperature                           No. Emulsion A                                                                           Emulsion B                                                                           A and B                                                                            (10.sup.-4 g/m.sup.2)                                                                 ity  tion                                                                              10° C.                                                                     20° C.                                                                     30° C.                                                                     Remarks                   __________________________________________________________________________     1  0.55 μm                                                                           0.85 μm                                                                           6:4  9.0      94   2.10*                                                                            2.03                                                                              2.11                                                                              2.45                                                                              Comparison                 2  0.55 μm                                                                           0.85 μm                                                                           6:4  8.0      88   2.12*                                                                            2.02                                                                              2.13                                                                              2.41                                                                              Comparison                 3  0.55 μm                                                                           0.85 μm                                                                           6:4  7.0      80   2.09*                                                                            2.01                                                                              2.10                                                                              2.16                                                                              Comparison                 4  0.55 μm                                                                           0.85 μm                                                                           6:4  6.0      72   2.10*                                                                            2.00                                                                              2.08                                                                              2.11                                                                              Comparison                 5  0.55 μm                                                                           0.85 μm                                                                           6:4  5.0      63   2.05*                                                                            2.00                                                                              2.02                                                                              2.07                                                                              Comparison                 6  0.65 μm                                                                           0.85 μm                                                                           6:4  9.0     114  2.65                                                                              2.48                                                                              2.67                                                                              3.06                                                                              Comparison                 7  0.65 μm                                                                           0.85 μm                                                                           6:4  8.0     107  2.73                                                                              2.54                                                                              2.70                                                                              2.95                                                                              Comparison                 8  0.65 μm                                                                           0.85 μm                                                                           6:4  7.0      99  2.80                                                                              2.78                                                                              2.81                                                                              2.84                                                                              Invention                  9  0.65 μm                                                                           0.85 μm                                                                           6:4  6.0      93  2.71                                                                              2.74                                                                              2.74                                                                              2.75                                                                              Invention                 10  0.65 μm                                                                           0.85 μm                                                                           6:4  5.0      81  2.70                                                                              2.69                                                                              2.71                                                                              2.75                                                                              Invention                 11  0.75 μm                                                                           0.85 μm                                                                           6:4  9.0     122  3.05                                                                              2.87                                                                              3.06                                                                              3.60                                                                              Comparison                12  0.75 μm                                                                           0.85 μm                                                                           6:4  8.0     115  3.11                                                                              2.99                                                                              3.14                                                                              3.55                                                                              Comparison                13  0.75 μm                                                                           0.85 μm                                                                           6:4  7.0     108  3.15                                                                              3.15                                                                              3.17                                                                              3.21                                                                              Invention                 14  0.75 μm                                                                           0.85 μm                                                                           6:4  6.0     100  3.20                                                                              3.13                                                                              3.19                                                                              3.23                                                                              Invention                 15  0.75 μm                                                                           0.85 μm                                                                           6:4  5.0      93  3.12                                                                              3.10                                                                              3.11                                                                              3.17                                                                              Invention                 16  0.75 μm                                                                           0.85 μm                                                                           6:4  4.0      85  3.07                                                                              3.02                                                                              3.06                                                                              3.10                                                                              Invention                 17  0.82 μm                                                                           0.85 μm                                                                           6:4  9.0     129  3.72                                                                              3.34                                                                              3.69                                                                              4.05                                                                              Comparison                18  0.82 μm                                                                           0.85 μm                                                                           6:4  8.0     120  3.68                                                                              3.45                                                                              3.70                                                                              4.11                                                                              Comparison                19  0.82 μm                                                                           0.85 μm                                                                           6:4  7.0     114  3.70                                                                              3.60                                                                              3.65                                                                              3.82                                                                              Comparison                20  0.82 μm                                                                           0.85 μm                                                                           6:4  6.0     105  3.75                                                                              3.66                                                                              3.72                                                                              3.81                                                                              Comparison                21  0.82 μm                                                                           0.85 μm                                                                           6:4  5.0     100  3.60                                                                              3.56                                                                              3.63                                                                              3.72                                                                              Comparison                22  0.65 μm                                                                           0.90 μm                                                                           7:3  8.0     110  2.81                                                                              2.65                                                                              2.84                                                                              3.25                                                                              Comparison                23  0.65 μm                                                                           0.90 μm                                                                           7:3  7.0     101  2.84                                                                              2.80                                                                              2.84                                                                              2.88                                                                              Invention                 24  0.65 μm                                                                           0.90 μm                                                                           7:3  6.0      95  2.88                                                                              2.83                                                                              2.87                                                                              2.92                                                                              Invention                 25  0.65 μm                                                                           0.90 μm                                                                           7:3  5.0      89  2.79                                                                              2.75                                                                              2.80                                                                              2.83                                                                              Invention                 26  0.75 μm                                                                           0.90 μm                                                                           7:3  8.0     116  3.24                                                                              3.08                                                                              3.21                                                                              3.64                                                                              Comparison                27  0.75 μm                                                                           0.90 μm                                                                           7:3  7.0     110  3.22                                                                              3.15                                                                              3.22                                                                              3.29                                                                              Invention                 28  0.75 μm                                                                           0.90 μm                                                                           7:3  6.0     104  3.22                                                                              3.14                                                                              3.19                                                                              3.24                                                                              Invention                 29  0.75 μm                                                                           0.90 μm                                                                           7:3  5.0      99  3.09                                                                              3.07                                                                              3.11                                                                              3.15                                                                              Invention                 30  0.75 μm                                                                           0.95 μm                                                                           7:3  8.0     132  2.29                                                                              2.10                                                                              2.30                                                                              2.55                                                                              Comparison                31  0.75 μm                                                                           0.95 μm                                                                           7:3  7.0     121  2.32                                                                              2.18                                                                              2.31                                                                              2.36                                                                              Comparison                32  0.75 μm                                                                           0.95 μm                                                                           7:3  6.0     113  2.35                                                                              2.22                                                                              2.33                                                                              2.37                                                                              Comparison                33  0.75 μm                                                                           0.95 μm                                                                           7:3  5.0     104  2.20                                                                              2.19                                                                              2.24                                                                              2.30                                                                              Comparison                __________________________________________________________________________     *Characteristic curve has a plateau at an intermediate density region.   

The following have been understood from the result in Table 1.

Samples 1-5 using the emulsion having the average grain size smallerthan the claimed value, 0.6 μm, in the blue sensitive layer is too lowerin both of the sensitivity and the gradation. Besides, Samples 30-33, inthe blue-sensitive layer of which an emulsion having an average grainsize larger than the upper limit of the claimed grain size, 0.9 μm, isused, are high in the sensitivity but undesirably too lower in thegradation because of lower developability thereof.

The samples in which the difference of the average grain size betweentwo emulsions used in the blue-sensitive emulsion layer is 0.05 μm orless, Sample Nos.17 to 21, are not suitable for the light-sensitivematerial for printing because the contrast is too high and the latitudeis too narrow.

Moreover, in the samples with the coating amount of the sensitizing dyefalling without of the range of the invention, the gradation isremarkably varied depending on the temperature at the time of exposureand insufficient in the stability in the gradation even though thesensitivity and gradation are sufficient under the ordinary condition.

On the other hand, the color light-sensitive material which wasexcellent in sensitivity and gradation and had gradation stabilityextremely excellent furthermore for the variation in temperature foundout the sample within the range in the combination of grain sizes in thepresent invention as for the coated amount of the sensitizing dye.

Example 2

Experiments were carried out in the same manner as in Example 1 exceptthat the kind of the sensitizing dye and the kind of the stabilizingagent in chemical ripening were changed like showing Table 2. The coatedamount of the stabilizing agent was adjusted to the same to STAB-1 usedby example 1 amount. The result was shown in the table.

                                      TABLE 2                                     __________________________________________________________________________    Average grain size           Coating amount   Gradation by                    Sam-                                                                             Emulsion                                                                            Emulsion     Kind of                                                                              of blue-                                                                              Relative exposure at various             ple                                                                              A (Mixing                                                                           B (Mixing                                                                           Kind of                                                                              sensitizing                                                                          sensitizing                                                                           Sensi-                                                                             Grada-                                                                            temperature                     No.                                                                              ratio 65%)                                                                          ratio 35%)                                                                          stabilizer                                                                           dye    (10.sup.-4 g/m.sup.2)                                                                 tivity                                                                             tion                                                                              10° C.                                                                     20° C.                                                                     30° C.                                                                     Remarks             __________________________________________________________________________    34 0.65 μm                                                                          0.86 μm                                                                          STB-1  BS-1   9.0     115  2.69                                                                              2.40                                                                              2.64                                                                              3.15                                                                              Comp.               35 0.65 μm                                                                          0.86 μm                                                                          STB-1  BS-1   7.0     100  2.82                                                                              2.76                                                                              2.80                                                                              2.85                                                                              Inv.                36 0.65 μm                                                                          0.86 μm                                                                          STB-1  BS-1   5.0      80  2.73                                                                              2.69                                                                              2.75                                                                              2.82                                                                              Inv.                37 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          BS-1   9.0     130  2.95                                                                              2.54                                                                              2.92                                                                              3.31                                                                              Comp.                              Exemplified                                                                   compound 1                                                     38 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          BS-1   7.0     113  3.01                                                                              2.94                                                                              3.00                                                                              3.10                                                                              Inv.                               Exemplified                                                                   compound I                                                     39 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          BS-1   5.0      92  2.94                                                                              2.90                                                                              2.91                                                                              2.97                                                                              Inv.                               Exemplified                                                                   compound 1                                                     40 0.65 μm                                                                          0.86 μm                                                                          STB-1  Exemplified                                                                          9.0     123  2.86                                                                              2.65                                                                              2.82                                                                              3.30                                                                              Comp.                                     compound                                                                      I-5                                                     41 0.65 μm                                                                          0.86 μm                                                                          STB-1  Exemplified                                                                          7.0     108  2.84                                                                              2.74                                                                              2.85                                                                              2.91                                                                              Inv.                                      compound                                                                      I-5                                                     42 0.65 μm                                                                          0.86 μm                                                                          STB-1  Exemplified                                                                          5.0      87  2.79                                                                              2.75                                                                              2.80                                                                              2.89                                                                              Inv.                                      compound                                                                      I-5                                                     43 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Exemplified                                                                          9.0     131  3.01                                                                              3.00                                                                              3.03                                                                              3.41                                                                              Comp.                              Exemplified                                                                          compound                                                               compound 1                                                                           I-5                                                     44 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Exemplified                                                                          7.0     119  3.14                                                                              3.12                                                                              3.16                                                                              3.23                                                                              Inv.                               Exemplified                                                                          compound                                                               compound 1                                                                           I-5                                                     45 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Exemplified                                                                          5.0     105  3.07                                                                              3.05                                                                              3.10                                                                              3.17                                                                              Inv.                               Exemplified                                                                          compound                                                               compound 1                                                                           I-5                                                     46 0.65 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           9.0     140  3.09                                                                              2.92                                                                              3.07                                                                              3.50                                                                              Comp.                                     exemplified                                                                   compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              47 0.65 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           7.0     123  3.17                                                                              3.10                                                                              3.15                                                                              3.21                                                                              Inv.                                      exemplified                                                                   compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              48 0.65 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           5.0     111  3.13                                                                              3.07                                                                              3.13                                                                              3.18                                                                              Inv.                                      exemplified                                                                   compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              49 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           9.0     165  3.12                                                                              3.06                                                                              3.13                                                                              3.49                                                                              Comp.                              Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              50 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           7.0     140  3.17                                                                              3.19                                                                              3.19                                                                              3.20                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              51 0.65 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           5.0     129  3.15                                                                              3.15                                                                              3.16                                                                              3.16                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              52 0.75 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           9.0     172  3.06                                                                              3.02                                                                              3.10                                                                              3.42                                                                              Comp.                                     exemplified                                                                   compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              53 0.75 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           7.0     144  3.15                                                                              3.14                                                                              3.17                                                                              3.20                                                                              Inv.                                      exemplified                                                                   compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              54 0.75 μm                                                                          0.86 μm                                                                          STB-1  Mixture of                                                                           5.0     125  3.11                                                                              3.09                                                                              3.12                                                                              3.16                                                                              Inv.                                      exemplified                                                                   compound                                                                      I-8/II-B                                                                      (mixing                                                                       ratio 2:8)                                              55 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           9.0     198  3.18                                                                              3.01                                                                              3.17                                                                              3.54                                                                              Comp.                              Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              56 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           7.0     175  3.25                                                                              3.24                                                                              3.26                                                                              3.26                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              57 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           5.0     156  3.17                                                                              3.19                                                                              3.18                                                                              3.19                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 1                                                                           compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              58 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           9.0     166  3.20                                                                              3.08                                                                              3.19                                                                              3.51                                                                              Comp.                              Exemplified                                                                          exemplified                                                            compound 26                                                                          compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              59 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           7.0     150  3.23                                                                              3.25                                                                              3.26                                                                              3.26                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 26                                                                          compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              60 0.75 μm                                                                          0.86 μm                                                                          Formula III                                                                          Mixture of                                                                           5.0     137  3.21                                                                              3.20                                                                              3.20                                                                              3.21                                                                              Inv.                               Exemplified                                                                          exemplified                                                            compound 26                                                                          compound                                                                      I-8/II-8                                                                      (mixing                                                                       ratio 2:8)                                              __________________________________________________________________________

It is found out from the results of Tables 7 and 8 that the sensitivity,the gradation and the stability of gradation to the variation of thetemperature at the time of exposure of the samples are sufficient whenthe mixed emulsion satisfying the requirements of the invention as tothe average grain size is used in the blue-sensitive emulsion layer.Such effects have been established also in Example 1.

Moreover, it is found that the gradation variation depending on thetemperature at the time of exposing is considerably lowered in SampleNos. 50, 51, 56, 57, 59 and 60 in which stabilizers of Formula 3 wereused together with the sensitizing dye. These samples also havesufficient sensitivity and gradation.

Example 3 P

Experiments shown in Examples 1 and 2 were repeated except that yellowcoupler YC-8 or Y-12 were used in place of the yellow coupler used inExamples 1 and 2.

As the results of the experiments, the same effects as in Examples 1 and2 were reproduced. Moreover, it was found that the samples wereexcellent because of the yellow couplers have sharp spectral adsorptionand superior in the color reproduction.

What is claimed is:
 1. A silver halide light-sensitive photographicmaterial comprising a support having thereon a blue-sensitive silverhalide emulsion layer comprising a mixture of at least two kinds ofsilver halide emulsions each optically sensitized with at least oneblue-sensitizing dye, wherein(1) said silver halide emulsions eachcomprise silver chloride grains or silver chlorobromide grains having asilver chloride content not less than 90 mol %, (2) said silver halideemulsions each have an average grain size, in terms of diameter ofspherical grain, being within the range of 0.6 μm to 0.9 μm and beingdifferent from each other in the average grain size by 0.07 μm to 0.15μm, and (3) a total coating amount of said at least one blue-sensitizingdye is not more than 7.0×10⁻⁴ g/m².
 2. The photographic material ofclaim 1, wherein said blue-sensitive emulsions are sensitized with a dyerepresented by the following Formula 1 and a dye represented by thefollowing Formula 2: ##STR29## wherein Z₁ and Z₂ are independently agroup of atoms necessary to complete a thiazole ring, a benzothiazolering, a benzoselenazole ring, a naphthothiazole ring or anaphthoselenazole ring; R₁ and R₂ are independently an aliphatic groupor an aliphatic group having a carboxyl group or a sulfo group providedthat at least one of R₁ and R₂ is an aliphatic group having a carboxylgroup or a sulfo group; X₁ is an acid anion: and m is an integer of 0 or1, ##STR30## wherein Z₃ and Z₄ are independently a group of atomsnecessary to complete a thiazole ring, a benzothiazole ring or abenzoselenazole ring; R₃ and R₄ are independently an aliphatic groupprovided that at least one of R₃ and R₄ is an aliphatic group having acarboxyl group or a sulfo group; X₂ is an acid anion: and n is aninteger of 0 or
 1. 3. The photographic material of claim 1, wherein theamount of said blue-sensitizing dye is 4.0×10⁻⁴ g/m² to 7.0×10⁻⁴ g/m².4. The photographic material of claim 1, wherein said photographicmaterial is a color photographic material further comprising agreen-sensitizing silver halide emulsion layer and a red-sensitivesilver halide emulsion layer.